1-Hexene hydroformylation with the rhodium(I) triphosphane complex [Rh(CO){PhP(CH2CH2PPh2)2}]PF 6: An in situ study using high-pressure NMR spectroscopy

Article abstract of DOI:10.1002/cber.19971301113

The rhodium-catalyzed hydroformylation of 1-hexene in THF with the linear triphosphane PhP(CH₂CH₂PPh₂)₂ [PP₂] has been studied both in situ and in high-pressure autoclaves. Sapphire NMR tubes with titanium valves have proved useful for studying the in situ reactions under conditions of relatively high syngas pressure (30-90 atm H₂/CO) and temperature (60-100 °C). Under conditions conducive to effective hydroformylation, the catalyst precursor [(PP₂)Rh(CO)]+ is quantitatively converted to the dicarbonyl [(PP₂)Rh(CO)₂]+, which is also the termination product of the catalysis. Irrespective of the syngas composition and of the total pressure, the dicarbonyl complex is the only phosphorus-containing species detectable on the NMR time-scale during the course of the isomerization and hydroformylation of the alkene. The PP₂-Rh catalytic system exhibits some peculiar features that may be summarized as follows, (i) Very high partial pressures of CO (120 atm) neither inhibit the hydroformylation nor af-feet the n/i selectivity; (ii) alkene hydrogenation occurs neither at very high partial pressures of H2 (120 atm) nor in the absence of added CO; (iii) the isomerization rate is slightly faster than that of hydroformylation; (iv) terminal and internal alkenes (2-, 3-hexenes) are hydroformylated with comparable rates. Various control experiments have been carried out using in-situ NMR, as well as batch experiments under different reaction conditions or with different catalyst precursors. Despite these extensive studies, unambiguous conclusions about the catalysis mechanism have not been reached. In particular, the possibility that different catalysts may be operative depending on the reaction conditions cannot be ruled out. The hydroformylation results rule out the involvement of phosphane-free "Rh-CO" catalysts, even under conditions of very high partial pressure of CO, and point to "(PP₂)Rh(CO)_x" catalysts with small steric hindrance over the whole range of syngas pressures investigated. WILEY-VCH Verlag GmbH, 1997.